Catalytic CO reduction using photogenerated hydrides

Tuning the "hydricity"

Patrick D. Achord, James Muckerman, Etsuko Fujita

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

Producing methanol from CO2 would make valuable fuel from potentially dangerous waste. Nature shows the way in its photosynthetic use of the hydride-donor NADPH. That molecule was the inspiration for Tanaka's pbn (pbn = 2-(2-pyridyl-benzo[b]-1.5-napthyridine), the doubly reduced/doubly protonated pbnHH form of which presumably electrocatalytically reduced acetone to isopropanol (Angew. Chem. Int. Ed. 2005, 44, 5891-5894). Fujita et al. prepared Ru(pbnHH)(bpy)2 2+ (bpy = 2,2'-bipyridine) by irradiating Ru(pbn)(bpy)2 2+ with visible light (Angew. Chem. Int. Ed. 2007, 46, 4169-4172). The mechanism involves pooling two photons in a disproportionation step (Fujita et al., Inorg. Chem. 2008, in press). Our DFT calculations indicate that it may be possible to harvest a third photon to form the triply reduced, doubly protonated Ru(pbnHH.-)(bpy)2 +. Our calculations also indicate that this molecule is sufficiently "hydritic" to reduce a metal-bound carbonyl on CpReNO(CO)2. Spin density calculations are consistent with the proposed mechanism.

Original languageEnglish
Title of host publicationACS National Meeting Book of Abstracts
Publication statusPublished - 2008
Event236th National Meeting and Exposition of the American Chemical Society, ACS 2008 - Philadelpia, PA, United States
Duration: Aug 17 2008Aug 21 2008

Other

Other236th National Meeting and Exposition of the American Chemical Society, ACS 2008
CountryUnited States
CityPhiladelpia, PA
Period8/17/088/21/08

Fingerprint

Hydrides
Tuning
Photons
2,2'-Dipyridyl
Molecules
2-Propanol
Acetone
NADP
Discrete Fourier transforms
Methanol
Metals
bis(bipyridyl)ruthenium(II)

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Catalytic CO reduction using photogenerated hydrides : Tuning the "hydricity". / Achord, Patrick D.; Muckerman, James; Fujita, Etsuko.

ACS National Meeting Book of Abstracts. 2008.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Achord, PD, Muckerman, J & Fujita, E 2008, Catalytic CO reduction using photogenerated hydrides: Tuning the "hydricity". in ACS National Meeting Book of Abstracts. 236th National Meeting and Exposition of the American Chemical Society, ACS 2008, Philadelpia, PA, United States, 8/17/08.
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